CN117487103B - Halogen-free high-temperature-resistant flame-retardant polymer material and preparation method thereof - Google Patents
Halogen-free high-temperature-resistant flame-retardant polymer material and preparation method thereof Download PDFInfo
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- CN117487103B CN117487103B CN202311843594.8A CN202311843594A CN117487103B CN 117487103 B CN117487103 B CN 117487103B CN 202311843594 A CN202311843594 A CN 202311843594A CN 117487103 B CN117487103 B CN 117487103B
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003063 flame retardant Substances 0.000 title claims abstract description 51
- 239000002861 polymer material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 101
- -1 polypropylene Polymers 0.000 claims abstract description 99
- 239000004743 Polypropylene Substances 0.000 claims abstract description 92
- 229920001155 polypropylene Polymers 0.000 claims abstract description 92
- 229920002748 Basalt fiber Polymers 0.000 claims abstract description 67
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 23
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 claims abstract description 21
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 15
- MRRXLWNSVYPSRB-UHFFFAOYSA-N ethenyl-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)C=C MRRXLWNSVYPSRB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 12
- QHJWOSHIGFDANE-UHFFFAOYSA-N prop-2-enylphosphane Chemical compound PCC=C QHJWOSHIGFDANE-UHFFFAOYSA-N 0.000 claims abstract description 12
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 147
- 238000003756 stirring Methods 0.000 claims description 130
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 97
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 41
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 37
- 235000019441 ethanol Nutrition 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 22
- 230000002378 acidificating effect Effects 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 19
- 239000012968 metallocene catalyst Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 13
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000007723 die pressing method Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- PUSKHXMZPOMNTQ-UHFFFAOYSA-N ethyl 2,1,3-benzoselenadiazole-5-carboxylate Chemical compound CCOC(=O)C1=CC=C2N=[Se]=NC2=C1 PUSKHXMZPOMNTQ-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 abstract description 30
- 238000006116 polymerization reaction Methods 0.000 abstract description 19
- 238000007731 hot pressing Methods 0.000 abstract description 3
- 238000007781 pre-processing Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005457 optimization Methods 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 229920002627 poly(phosphazenes) Polymers 0.000 description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006276 transfer reaction Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a halogen-free high-temperature-resistant flame-retardant polymer material and a preparation method thereof, and relates to the technical field of polymer materials. When the halogen-free high-temperature-resistant flame-retardant polymer material is prepared, 3-aminopropyl triethoxysilane is used for preprocessing chopped basalt fibers, and then the chopped basalt fibers react with 1, 3-bis (3-aminopropyl) tetramethyl disiloxane and allyl phosphine dichloride to prepare modified chopped basalt fibers; after the allyl alcohol is protected by triisobutylaluminum, the allyl alcohol and vinyl pentamethyl disiloxane participate in polymerization of propylene together to prepare pre-modified polypropylene, and the pre-modified polypropylene reacts with maleic anhydride to prepare modified polypropylene; and (3) melting, mixing and extruding the modified chopped basalt fiber, the modified polypropylene and the potassium persulfate, putting the mixture into a die for hot pressing, and taking out the mixture after cooling to obtain the halogen-free high-temperature-resistant flame-retardant polymer material. The halogen-free high-temperature-resistant flame-retardant polymer material prepared by the invention has good tensile strength, high-temperature-resistant anti-dripping performance and flame-retardant performance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a halogen-free high-temperature-resistant flame-retardant high polymer material and a preparation method thereof.
Background
Polypropylene, which is one of five general plastics, has the advantages of good transparency, light weight, excellent insulation, strong corrosion resistance and the like, and is widely applied to the fields of household products, transportation, medical appliances, electronic devices and the like. In recent years, the polypropylene industry has further evolved rapidly and has a higher growing demand in the future, thanks to the ever-increasing production technologies and ever-expanding application fields. The polypropylene consists of pure hydrocarbon elements, and the molecular chain is of a carbon-carbon single bond linear structure, so that the polypropylene is easy to burn, a large amount of molten drops are generated in the burning process, secondary ignition is further initiated and the burning range is enlarged, and the polypropylene has huge hidden danger to property safety of people.
The flammability of polypropylene has greatly limited its use in many applications, which has become a major limitation in the development of polypropylene, and the dripping behavior of polypropylene is also an important aspect affecting the combustion hazard of polypropylene. The root cause of the serious polypropylene dripping phenomenon is that the melting point is far lower than the degradation temperature, and the high temperature generated by combustion causes the matrix to be extremely easy to soften to form dripping. Therefore, it is necessary to modify polypropylene to improve the flame retardancy of polypropylene, and to make it have a good stable structure at high temperature without dripping.
Disclosure of Invention
The invention aims to provide a halogen-free high-temperature-resistant flame-retardant polymer material and a preparation method thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the halogen-free high-temperature-resistant flame-retardant polymer material is prepared by melting, mixing and extruding modified chopped basalt fiber, modified polypropylene and potassium persulfate, hot-pressing in a die, cooling and taking out.
As optimization, the modified chopped basalt fiber is prepared by pretreating chopped basalt fiber by 3-aminopropyl triethoxysilane and then reacting with 1, 3-bis (3-aminopropyl) tetramethyl disiloxane and allyl phosphine dichloride.
As optimization, the modified polypropylene is prepared by protecting the allyl alcohol with triisobutyl aluminum, then, jointly participating in polymerization of propylene with vinyl pentamethyl disiloxane to prepare the pre-modified polypropylene, and reacting the pre-modified polypropylene with maleic anhydride.
The preparation method of the halogen-free high-temperature-resistant flame-retardant polymer material comprises the following preparation steps:
(1) Absolute ethyl alcohol and 8-12% hydrochloric acid aqueous solution in mass ratio of 1: 2-3, uniformly mixing to prepare an acidic ethanol solution; in a nitrogen atmosphere, hydroxyl protecting monomer, vinyl pentamethyl disiloxane and toluene are mixed according to the mass ratio of 1:1: mixing 30-40, adding the mixture into a reaction container, stirring at 10-20 ℃ for 20-30 min at 200-300 r/min, introducing propylene to remove nitrogen, enabling the propylene pressure in the reaction container to reach and be maintained at 0.11-0.13 MPa, adding a catalyst solution with the mass of 0.03-0.04 times of that of toluene, stirring at 70-80 ℃ for 4-6 h at 200-300 r/min, pouring an acidic ethanol solution with the mass of 4-5 times of that of toluene after the reaction is finished, stirring at 10-30 ℃ for 20-30 min at 200-300 r/min, filtering, washing 3-5 times by using absolute ethanol, and drying at 70-80 ℃ for 8-10 h to obtain pre-modified polypropylene;
(2) In a nitrogen atmosphere, pre-modified polypropylene and toluene are mixed according to the mass ratio of 1: uniformly mixing 40-50, stirring at 70-80 ℃ for 10-15 min at 200-300 r/min, continuously stirring, adding maleic anhydride with the mass of 0.2-0.3 times of that of the pre-modified polypropylene at a constant speed within 20-30 min, continuously stirring for 3-4 h after the addition, pouring the mixture into pure water with the mass of 200-250 times of that of the pre-modified polypropylene after the reaction is finished, stirring at 10-30 ℃ for 20-30 min at 200-300 r/min, filtering, washing for 3-5 times by using absolute ethyl alcohol, and drying at 70-80 ℃ for 8-10 h to obtain modified polypropylene;
(3) The preparation method comprises the following steps of (1) mixing chopped basalt fibers, 3-aminopropyl triethoxysilane, absolute ethyl alcohol and 10-12% ammonia water according to a mass ratio of 1:1: 2-3: uniformly mixing 8-10, and stirring at 20-30 ℃ and 200-300 r/min for 2-3 hours to obtain pretreated chopped basalt fibers; pretreating chopped basalt fiber, 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:0.3 to 0.4:0.4 to 0.6: 8-10, uniformly mixing, adding allyl phosphine dichloride with the molar weight of 0.9-0.95 times of that of 1, 3-bis (3-aminopropyl) tetramethyl disiloxane at a constant speed within 50-60 min under the stirring condition of 0-5 ℃ and 200-300 r/min in a nitrogen atmosphere, continuously stirring for 2-3 hours after the addition is finished, heating to 30-40 ℃, continuously stirring for reacting for 4-6 hours, mechanically separating, washing for 3-5 times by pure water, and drying for 8-10 hours at 60-70 ℃ to obtain modified chopped basalt fibers;
(4) The modified chopped basalt fiber, modified polypropylene and potassium persulfate are mixed according to the mass ratio of 1: 8-9: and (3) uniformly mixing 0.01-0.02, placing in a double-screw extruder, melting, mixing and extruding at 190-200 ℃, placing in a die, die pressing at 190-200 ℃ and 0.3-0.4 MPa for 10-15 s, keeping the pressure unchanged, cooling to 80-90 ℃, standing for 20-24 h, and naturally cooling to room temperature to obtain the halogen-free high-temperature-resistant flame-retardant polymer material.
As optimization, the preparation method of the hydroxyl protecting monomer in the step (1) comprises the following steps: uniformly mixing an equimolar amount of acrylic alcohol and triisobutyl aluminum in a nitrogen atmosphere, stirring for 20-30 min at-70 to-60 ℃ at 200-300 r/min, heating to room temperature, and continuously stirring for 3-4 h to obtain a hydroxyl-protected monomer;
the reaction process is as follows:
。
as an optimization, the catalyst solution in the step (2) is prepared by mixing a metallocene catalyst, 2, 6-di-tert-butyl-4-methylphenol and toluene according to a mass ratio of 1:0.3 to 0.4: 6-8, uniformly mixing, and stirring for 20-30 min at the temperature of 20-30 ℃ and the speed of 200-300 r/min to prepare a catalyst solution; the model of the metallocene catalyst is M1810HA.
As an optimization, the reaction process of the pre-modified polypropylene in the step (1) is as follows:
。
as an optimization, the reaction process of the modified polypropylene in the step (2) is as follows:
。
as optimization, the diameter of the chopped basalt fiber in the step (3) is 12.7 mu m, the length is 6mm, and the linear density is 200tex.
As optimization, the modified structure of the modified chopped basalt fiber in the step (3) is as follows:
。
compared with the prior art, the invention has the following beneficial effects:
when the halogen-free high-temperature-resistant flame-retardant high polymer material is prepared, after the allyl alcohol is protected by triisobutyl aluminum, the allyl alcohol and vinyl pentamethyl disiloxane participate in polymerization of propylene together to prepare pre-modified polypropylene, and the pre-modified polypropylene reacts with maleic anhydride to prepare modified polypropylene; and (3) melting, mixing and extruding the modified chopped basalt fiber, the modified polypropylene and the potassium persulfate, putting the mixture into a die for hot pressing, and taking out the mixture after cooling to obtain the halogen-free high-temperature-resistant flame-retardant polymer material.
Firstly, the allyl alcohol and vinyl pentamethyl disiloxane participate in propylene polymerization together and are catalyzed and polymerized by a metallocene catalyst, because the allyl alcohol is a polar monomer, alcohols in the structure can act with the active center of the metallocene catalyst to inhibit the insertion of the monomer, so that the polymerization activity is reduced, the embedded copolymerization effect of the allyl alcohol is affected, the allyl alcohol is protected, the polymerization process can be better carried out, more hydroxyl groups are easier to connect, and the allyl alcohol can be combined with more maleic anhydride subsequently, so that the tensile strength and the high-temperature-resistant anti-dripping performance are improved; in addition, the alkyl aluminum component in the metallocene catalyst can cause chain transfer reaction to lose active polymerization characteristics of the system, and the steric hindrance effect of the 2, 6-di-tert-butyl-4-methylphenol is used to avoid the chain transfer reaction caused by the alkyl aluminum component in the metallocene catalyst to lose active polymerization characteristics of the system, so that the active polymerization of propylene and polar monomers is improved, and more hydroxyl groups are more easily connected; vinyl pentamethyl disiloxane is added in the polymerization process to participate in copolymerization, and a silica structure is introduced, so that the thermal stability of the modified polypropylene is improved, and the high-temperature resistance and the anti-dripping performance are further improved; the pre-modified polypropylene is modified by maleic anhydride, carboxyl and double bond are formed on the modified polypropylene, the carboxyl can be combined with amino on the modified chopped basalt fiber electrostatically, or is dehydrated to form amide combination, and the double bond can initiate polymerization of free radical unsaturated bond by potassium persulfate.
Secondly, 3-aminopropyl triethoxy silane is used for preprocessing chopped basalt fiber, and then the chopped basalt fiber is reacted with 1, 3-bis (3-aminopropyl) tetramethyl disiloxane and allyl phosphine dichloride to prepare modified chopped basalt fiber, a polyphosphazene organosilicon branched chain is generated on the surface of the chopped basalt fiber, the modified chopped basalt fiber contains a large amount of phosphorus, silicon and nitrogen elements, the modified chopped basalt fiber has good flame retardant property, amino groups on the polyphosphazene organosilicon branched chain can be combined with carboxyl groups on modified polypropylene polymerization, and double bonds on the polyphosphazene organosilicon branched chain can participate in polymerization of free radical unsaturated bonds to form a crosslinked network structure, so that the flame retardant property, tensile strength and high temperature resistance and anti-droplet property are improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The method provided by the present invention is described in detail by the following examples for more clarity of illustration.
Example 1
The preparation method of the halogen-free high-temperature-resistant flame-retardant polymer material mainly comprises the following preparation steps:
(1) Absolute ethyl alcohol and 8% hydrochloric acid aqueous solution by mass ratio 1:2, uniformly mixing to prepare an acidic ethanol solution; uniformly mixing an equimolar amount of propylene alcohol and triisobutyl aluminum in a nitrogen atmosphere, stirring for 30min at the temperature of-70 ℃ at the speed of 200r/min, heating to room temperature and continuously stirring for 3h to prepare a hydroxyl-protected monomer; the method comprises the steps of (1) mixing an M1810HA metallocene catalyst, 2, 6-di-tert-butyl-4-methylphenol and toluene according to a mass ratio of 1:0.3:6, uniformly mixing, and stirring for 30min at 20 ℃ and 200r/min to prepare a catalyst solution; in a nitrogen atmosphere, hydroxyl protecting monomer, vinyl pentamethyl disiloxane and toluene are mixed according to the mass ratio of 1:1:30, uniformly mixing, adding the mixture into a reaction container, stirring at 10 ℃ for 30min at 200r/min, introducing propylene to remove nitrogen, enabling the propylene pressure in the reaction container to reach and maintain at 0.11MPa, adding a catalyst solution with the mass 0.03 times of that of toluene, stirring at 70 ℃ for 6h at 200r/min, pouring an acidic ethanol solution with the mass 4 times of that of toluene after the reaction is finished, stirring at 10 ℃ for 30min at 200r/min, filtering, washing for 3 times by using absolute ethanol, and drying at 70 ℃ for 10h to obtain pre-modified polypropylene;
(2) In a nitrogen atmosphere, pre-modified polypropylene and toluene are mixed according to the mass ratio of 1:40, stirring for 15min at 70 ℃ at 200r/min, continuously stirring, adding maleic anhydride with the mass of 0.2 times of that of the pre-modified polypropylene at a constant speed within 20min, continuously stirring for 3h after the addition, pouring into pure water with the mass of 200 times of that of the pre-modified polypropylene after the reaction, stirring for 30min at 10 ℃ at 200r/min, filtering, washing for 3 times with absolute ethyl alcohol, and drying for 10h at 70 ℃ to obtain modified polypropylene;
(3) The preparation method comprises the following steps of (1) mixing chopped basalt fibers, 3-aminopropyl triethoxysilane, absolute ethyl alcohol and 10% ammonia water according to a mass ratio of 1:1:2:8, uniformly mixing, and stirring for 3 hours at 20 ℃ and 200r/min to obtain the pretreated chopped basalt fiber; pretreating chopped basalt fiber, 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:0.3:0.4:8, uniformly mixing, adding allyl phosphine dichloride with the molar quantity of 1, 3-bis (3-aminopropyl) tetramethyl disiloxane being 0.9 times at a constant speed within 60min under the stirring condition of 200r/min at the temperature of 0 ℃ in a nitrogen atmosphere, continuously stirring for 3 hours after the addition is finished, heating to 30 ℃, continuously stirring for reaction for 6 hours, mechanically separating, washing with pure water for 3 times, and drying for 10 hours at the temperature of 60 ℃ to obtain modified chopped basalt fibers;
(4) The modified chopped basalt fiber, modified polypropylene and potassium persulfate are mixed according to the mass ratio of 1:8: and (3) uniformly mixing 0.01, placing in a double-screw extruder, melting, mixing and extruding at 190 ℃, placing in a die, die-pressing at 190 ℃ and 0.3MPa for 15s, keeping the pressure unchanged, cooling to 80 ℃, standing for 24h, and naturally cooling to room temperature to obtain the halogen-free high-temperature-resistant flame-retardant polymer material.
Example 2
The preparation method of the halogen-free high-temperature-resistant flame-retardant polymer material mainly comprises the following preparation steps:
(1) Absolute ethyl alcohol and hydrochloric acid aqueous solution with mass fraction of 10% are mixed according to mass ratio of 1:2.5, uniformly mixing to prepare an acidic ethanol solution; uniformly mixing an equimolar amount of propylene alcohol and triisobutyl aluminum in a nitrogen atmosphere, stirring at-65 ℃ for 25min at 250r/min, heating to room temperature and continuously stirring for 3.5h to obtain a hydroxyl-protected monomer; the method comprises the steps of (1) mixing an M1810HA metallocene catalyst, 2, 6-di-tert-butyl-4-methylphenol and toluene according to a mass ratio of 1:0.35:7, uniformly mixing, and stirring at 25 ℃ and 250r/min for 25min to prepare a catalyst solution; in a nitrogen atmosphere, hydroxyl protecting monomer, vinyl pentamethyl disiloxane and toluene are mixed according to the mass ratio of 1:1:35, uniformly mixing, adding into a reaction container, stirring at 15 ℃ for 25min at 250r/min, introducing propylene to remove nitrogen, enabling the propylene pressure in the reaction container to reach and maintain at 0.12MPa, adding a catalyst solution with the mass of 0.035 times of that of toluene, stirring at 75 ℃ for 5h at 250r/min, pouring an acidic ethanol solution with the mass of 4.5 times of that of toluene after the reaction is finished, stirring at 20 ℃ for 25min at 250r/min, filtering, washing for 4 times by using absolute ethanol, and drying at 75 ℃ for 9h to obtain pre-modified polypropylene;
(2) In a nitrogen atmosphere, pre-modified polypropylene and toluene are mixed according to the mass ratio of 1:45, stirring for 12min at 75 ℃ at 250r/min, continuously stirring, adding maleic anhydride with the mass of 0.25 times of that of the pre-modified polypropylene at a constant speed within 25min, continuously stirring for 3.5h after the addition, pouring the mixture into pure water with the mass of 225 times of that of the pre-modified polypropylene after the reaction, stirring for 25min at 20 ℃ at 250r/min, filtering, washing for 4 times by absolute ethyl alcohol, and drying for 9h at 75 ℃ to obtain modified polypropylene;
(3) The preparation method comprises the following steps of (1) mixing chopped basalt fibers, 3-aminopropyl triethoxysilane, absolute ethyl alcohol and 11% ammonia water according to a mass ratio of 1:1:2.5:9, uniformly mixing, and stirring at 25 ℃ and 250r/min for 2.5 hours to obtain the pretreated chopped basalt fiber; pretreating chopped basalt fiber, 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:0.35:0.45:9, uniformly mixing, adding allyl phosphine dichloride with the molar quantity of 0.92 times of 1, 3-bis (3-aminopropyl) tetramethyl disiloxane at a constant speed within 55min under the stirring condition of 3 ℃ and 250r/min in a nitrogen atmosphere, continuously stirring for 2.5h after the addition is finished, heating to 35 ℃, continuously stirring for reacting for 5h, mechanically separating, washing for 4 times with pure water, and drying for 9h at 65 ℃ to obtain modified chopped basalt fibers;
(4) The modified chopped basalt fiber, modified polypropylene and potassium persulfate are mixed according to the mass ratio of 1:8.5: and (3) uniformly mixing 0.015, placing in a double-screw extruder, melting, mixing and extruding at 195 ℃, placing in a die, die-pressing at 195 ℃ and 0.35MPa for 12s, keeping the pressure unchanged, cooling to 85 ℃, standing for 22h, and naturally cooling to room temperature to obtain the halogen-free high-temperature-resistant flame-retardant polymer material.
Example 3
The preparation method of the halogen-free high-temperature-resistant flame-retardant polymer material mainly comprises the following preparation steps:
(1) Absolute ethyl alcohol and hydrochloric acid aqueous solution with the mass fraction of 12% are mixed according to the mass ratio of 1:3, uniformly mixing to prepare an acidic ethanol solution; uniformly mixing an equimolar amount of propylene alcohol and triisobutyl aluminum in a nitrogen atmosphere, stirring for 20min at the temperature of-60 ℃ at the speed of 300r/min, heating to room temperature and continuously stirring for 4h to prepare a hydroxyl-protected monomer; the method comprises the steps of (1) mixing an M1810HA metallocene catalyst, 2, 6-di-tert-butyl-4-methylphenol and toluene according to a mass ratio of 1:0.4:8, uniformly mixing, and stirring at 30 ℃ and 300r/min for 20min to prepare a catalyst solution; in a nitrogen atmosphere, hydroxyl protecting monomer, vinyl pentamethyl disiloxane and toluene are mixed according to the mass ratio of 1:1:40, uniformly mixing, adding the mixture into a reaction container, stirring at 20 ℃ for 20min at 300r/min, introducing propylene to remove nitrogen, enabling the propylene pressure in the reaction container to reach and maintain at 0.13MPa, adding a catalyst solution with the mass 0.04 times that of toluene, stirring at 80 ℃ for 4h at 300r/min, pouring an acidic ethanol solution with the mass 5 times that of toluene after the reaction is finished, stirring at 30 ℃ for 20min at 300r/min, filtering, washing for 5 times by using absolute ethanol, and drying at 80 ℃ for 8h to obtain pre-modified polypropylene;
(2) In a nitrogen atmosphere, pre-modified polypropylene and toluene are mixed according to the mass ratio of 1:50, stirring for 10min at 80 ℃ at 300r/min, continuously stirring, adding maleic anhydride with the mass of 0.3 times of that of the pre-modified polypropylene at a constant speed within 30min, continuously stirring for 3h after the addition, pouring the mixture into pure water with the mass of 250 times of that of the pre-modified polypropylene after the reaction, stirring for 20min at 30 ℃ at 300r/min, filtering, washing for 5 times with absolute ethyl alcohol, and drying for 8h at 80 ℃ to obtain modified polypropylene;
(3) The preparation method comprises the following steps of (1) mixing chopped basalt fibers, 3-aminopropyl triethoxysilane, absolute ethyl alcohol and 12% ammonia water according to a mass ratio of 1:1:3:10, uniformly mixing, and stirring for 2 hours at 30 ℃ and 300r/min to obtain the pretreated chopped basalt fiber; pretreating chopped basalt fiber, 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:0.4:0.6:10, uniformly mixing, adding allyl phosphine dichloride with the molar quantity of 0.95 times of 1, 3-bis (3-aminopropyl) tetramethyl disiloxane at a constant speed within 60min under the stirring condition of 5 ℃ and 300r/min in a nitrogen atmosphere, continuously stirring for 2h after the addition is finished, heating to 40 ℃, continuously stirring for reacting for 4h, mechanically separating, washing with pure water for 3 times, and drying at 70 ℃ for 8h to obtain modified chopped basalt fibers;
(4) The modified chopped basalt fiber, modified polypropylene and potassium persulfate are mixed according to the mass ratio of 1:9:0.02, placing in a double screw extruder, melting, mixing and extruding at 200 ℃, placing in a die, die-pressing at 200 ℃ and 0.4MPa for 10s, keeping the pressure unchanged, cooling to 90 ℃, standing for 20h, and naturally cooling to room temperature to obtain the halogen-free high-temperature-resistant flame-retardant polymer material.
Comparative example 1
The preparation method of the halogen-free high-temperature-resistant flame-retardant polymer material mainly comprises the following preparation steps:
(1) The method comprises the steps of mixing a metallocene catalyst, 2, 6-di-tert-butyl-4-methylphenol and toluene according to a mass ratio of 1:0.35:7, uniformly mixing, and stirring at 25 ℃ and 250r/min for 25min to prepare a catalyst solution; in a nitrogen atmosphere, mixing allyl alcohol, vinyl pentamethyl disiloxane and toluene according to a mass ratio of 1:1:35, uniformly mixing, adding into a reaction container, stirring at 15 ℃ for 25min at 250r/min, introducing propylene to remove nitrogen, enabling the propylene pressure in the reaction container to reach and maintain at 0.12MPa, adding a catalyst solution with the mass of 0.035 times of that of toluene, stirring at 75 ℃ for 5h at 250r/min, pouring an acidic ethanol solution with the mass of 4.5 times of that of toluene after the reaction is finished, stirring at 20 ℃ for 25min at 250r/min, filtering, washing for 4 times by using absolute ethanol, and drying at 75 ℃ for 9h to obtain pre-modified polypropylene;
(2) In a nitrogen atmosphere, pre-modified polypropylene and toluene are mixed according to the mass ratio of 1:45, stirring for 12min at 75 ℃ at 250r/min, continuously stirring, adding maleic anhydride with the mass of 0.25 times of that of the pre-modified polypropylene at a constant speed within 25min, continuously stirring for 3.5h after the addition, pouring the mixture into pure water with the mass of 225 times of that of the pre-modified polypropylene after the reaction, stirring for 25min at 20 ℃ at 250r/min, filtering, washing for 4 times by absolute ethyl alcohol, and drying for 9h at 75 ℃ to obtain modified polypropylene;
(3) The preparation method comprises the following steps of (1) mixing chopped basalt fibers, 3-aminopropyl triethoxysilane, absolute ethyl alcohol and 11% ammonia water according to a mass ratio of 1:1:2.5:9, uniformly mixing, and stirring at 25 ℃ and 250r/min for 2.5 hours to obtain the pretreated chopped basalt fiber; pretreating chopped basalt fiber, 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:0.35:0.45:9, uniformly mixing, adding allyl phosphine dichloride with the molar quantity of 0.92 times of 1, 3-bis (3-aminopropyl) tetramethyl disiloxane at a constant speed within 55min under the stirring condition of 3 ℃ and 250r/min in a nitrogen atmosphere, continuously stirring for 2.5h after the addition is finished, heating to 35 ℃, continuously stirring for reacting for 5h, mechanically separating, washing for 4 times with pure water, and drying for 9h at 65 ℃ to obtain modified chopped basalt fibers;
(4) The modified chopped basalt fiber, modified polypropylene and potassium persulfate are mixed according to the mass ratio of 1:8.5: and (3) uniformly mixing 0.015, placing in a double-screw extruder, melting, mixing and extruding at 195 ℃, placing in a die, die-pressing at 195 ℃ and 0.35MPa for 12s, keeping the pressure unchanged, cooling to 85 ℃, standing for 22h, and naturally cooling to room temperature to obtain the halogen-free high-temperature-resistant flame-retardant polymer material.
Comparative example 2
The preparation method of the halogen-free high-temperature-resistant flame-retardant polymer material mainly comprises the following preparation steps:
(1) Absolute ethyl alcohol and hydrochloric acid aqueous solution with mass fraction of 10% are mixed according to mass ratio of 1:2.5, uniformly mixing to prepare an acidic ethanol solution; uniformly mixing an equimolar amount of propylene alcohol and triisobutyl aluminum in a nitrogen atmosphere, stirring at-65 ℃ for 25min at 250r/min, heating to room temperature and continuously stirring for 3.5h to obtain a hydroxyl-protected monomer; the method comprises the steps of (1) mixing an M1810HA metallocene catalyst with toluene according to a mass ratio of 1:7, uniformly mixing, and stirring at 25 ℃ and 250r/min for 25min to prepare a catalyst solution; in a nitrogen atmosphere, hydroxyl protecting monomer, vinyl pentamethyl disiloxane and toluene are mixed according to the mass ratio of 1:1:35, uniformly mixing, adding into a reaction container, stirring at 15 ℃ for 25min at 250r/min, introducing propylene to remove nitrogen, enabling the propylene pressure in the reaction container to reach and maintain at 0.12MPa, adding a catalyst solution with the mass of 0.035 times of that of toluene, stirring at 75 ℃ for 5h at 250r/min, pouring an acidic ethanol solution with the mass of 4.5 times of that of toluene after the reaction is finished, stirring at 20 ℃ for 25min at 250r/min, filtering, washing for 4 times by using absolute ethanol, and drying at 75 ℃ for 9h to obtain pre-modified polypropylene;
(2) In a nitrogen atmosphere, pre-modified polypropylene and toluene are mixed according to the mass ratio of 1:45, stirring for 12min at 75 ℃ at 250r/min, continuously stirring, adding maleic anhydride with the mass of 0.25 times of that of the pre-modified polypropylene at a constant speed within 25min, continuously stirring for 3.5h after the addition, pouring the mixture into pure water with the mass of 225 times of that of the pre-modified polypropylene after the reaction, stirring for 25min at 20 ℃ at 250r/min, filtering, washing for 4 times by absolute ethyl alcohol, and drying for 9h at 75 ℃ to obtain modified polypropylene;
(3) The preparation method comprises the following steps of (1) mixing chopped basalt fibers, 3-aminopropyl triethoxysilane, absolute ethyl alcohol and 11% ammonia water according to a mass ratio of 1:1:2.5:9, uniformly mixing, and stirring at 25 ℃ and 250r/min for 2.5 hours to obtain the pretreated chopped basalt fiber; pretreating chopped basalt fiber, 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:0.35:0.45:9, uniformly mixing, adding allyl phosphine dichloride with the molar quantity of 0.92 times of 1, 3-bis (3-aminopropyl) tetramethyl disiloxane at a constant speed within 55min under the stirring condition of 3 ℃ and 250r/min in a nitrogen atmosphere, continuously stirring for 2.5h after the addition is finished, heating to 35 ℃, continuously stirring for reacting for 5h, mechanically separating, washing for 4 times with pure water, and drying for 9h at 65 ℃ to obtain modified chopped basalt fibers;
(4) The modified chopped basalt fiber, modified polypropylene and potassium persulfate are mixed according to the mass ratio of 1:8.5: and (3) uniformly mixing 0.015, placing in a double-screw extruder, melting, mixing and extruding at 195 ℃, placing in a die, die-pressing at 195 ℃ and 0.35MPa for 12s, keeping the pressure unchanged, cooling to 85 ℃, standing for 22h, and naturally cooling to room temperature to obtain the halogen-free high-temperature-resistant flame-retardant polymer material.
Comparative example 3
The preparation method of the halogen-free high-temperature-resistant flame-retardant polymer material mainly comprises the following preparation steps:
(1) Absolute ethyl alcohol and hydrochloric acid aqueous solution with mass fraction of 10% are mixed according to mass ratio of 1:2.5, uniformly mixing to prepare an acidic ethanol solution; uniformly mixing an equimolar amount of propylene alcohol and triisobutyl aluminum in a nitrogen atmosphere, stirring at-65 ℃ for 25min at 250r/min, heating to room temperature and continuously stirring for 3.5h to obtain a hydroxyl-protected monomer; the method comprises the steps of (1) mixing an M1810HA metallocene catalyst, 2, 6-di-tert-butyl-4-methylphenol and toluene according to a mass ratio of 1:0.35:7, uniformly mixing, and stirring at 25 ℃ and 250r/min for 25min to prepare a catalyst solution; in a nitrogen atmosphere, hydroxyl protecting monomers and toluene are mixed according to the mass ratio of 1:35, uniformly mixing, adding into a reaction container, stirring at 15 ℃ for 25min at 250r/min, introducing propylene to remove nitrogen, enabling the propylene pressure in the reaction container to reach and maintain at 0.12MPa, adding a catalyst solution with the mass of 0.035 times of that of toluene, stirring at 75 ℃ for 5h at 250r/min, pouring an acidic ethanol solution with the mass of 4.5 times of that of toluene after the reaction is finished, stirring at 20 ℃ for 25min at 250r/min, filtering, washing for 4 times by using absolute ethanol, and drying at 75 ℃ for 9h to obtain pre-modified polypropylene;
(2) In a nitrogen atmosphere, pre-modified polypropylene and toluene are mixed according to the mass ratio of 1:45, stirring for 12min at 75 ℃ at 250r/min, continuously stirring, adding maleic anhydride with the mass of 0.25 times of that of the pre-modified polypropylene at a constant speed within 25min, continuously stirring for 3.5h after the addition, pouring the mixture into pure water with the mass of 225 times of that of the pre-modified polypropylene after the reaction, stirring for 25min at 20 ℃ at 250r/min, filtering, washing for 4 times by absolute ethyl alcohol, and drying for 9h at 75 ℃ to obtain modified polypropylene;
(3) The preparation method comprises the following steps of (1) mixing chopped basalt fibers, 3-aminopropyl triethoxysilane, absolute ethyl alcohol and 11% ammonia water according to a mass ratio of 1:1:2.5:9, uniformly mixing, and stirring at 25 ℃ and 250r/min for 2.5 hours to obtain the pretreated chopped basalt fiber; pretreating chopped basalt fiber, 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:0.35:0.45:9, uniformly mixing, adding allyl phosphine dichloride with the molar quantity of 0.92 times of 1, 3-bis (3-aminopropyl) tetramethyl disiloxane at a constant speed within 55min under the stirring condition of 3 ℃ and 250r/min in a nitrogen atmosphere, continuously stirring for 2.5h after the addition is finished, heating to 35 ℃, continuously stirring for reacting for 5h, mechanically separating, washing for 4 times with pure water, and drying for 9h at 65 ℃ to obtain modified chopped basalt fibers;
(4) The modified chopped basalt fiber, modified polypropylene and potassium persulfate are mixed according to the mass ratio of 1:8.5: and (3) uniformly mixing 0.015, placing in a double-screw extruder, melting, mixing and extruding at 195 ℃, placing in a die, die-pressing at 195 ℃ and 0.35MPa for 12s, keeping the pressure unchanged, cooling to 85 ℃, standing for 22h, and naturally cooling to room temperature to obtain the halogen-free high-temperature-resistant flame-retardant polymer material.
Comparative example 4
The preparation method of the halogen-free high-temperature-resistant flame-retardant polymer material mainly comprises the following preparation steps:
(1) Absolute ethyl alcohol and hydrochloric acid aqueous solution with mass fraction of 10% are mixed according to mass ratio of 1:2.5, uniformly mixing to prepare an acidic ethanol solution; uniformly mixing an equimolar amount of propylene alcohol and triisobutyl aluminum in a nitrogen atmosphere, stirring at-65 ℃ for 25min at 250r/min, heating to room temperature and continuously stirring for 3.5h to obtain a hydroxyl-protected monomer; the method comprises the steps of (1) mixing an M1810HA metallocene catalyst, 2, 6-di-tert-butyl-4-methylphenol and toluene according to a mass ratio of 1:0.35:7, uniformly mixing, and stirring at 25 ℃ and 250r/min for 25min to prepare a catalyst solution; in a nitrogen atmosphere, hydroxyl protecting monomer, vinyl pentamethyl disiloxane and toluene are mixed according to the mass ratio of 1:1:35, uniformly mixing, adding into a reaction container, stirring at 15 ℃ for 25min at 250r/min, introducing propylene to remove nitrogen, enabling the propylene pressure in the reaction container to reach and maintain at 0.12MPa, adding a catalyst solution with the mass of 0.035 times of that of toluene, stirring at 75 ℃ for 5h at 250r/min, pouring an acidic ethanol solution with the mass of 4.5 times of that of toluene after the reaction is finished, stirring at 20 ℃ for 25min at 250r/min, filtering, washing for 4 times by using absolute ethanol, and drying at 75 ℃ for 9h to obtain modified polypropylene;
(2) The preparation method comprises the following steps of (1) mixing chopped basalt fibers, 3-aminopropyl triethoxysilane, absolute ethyl alcohol and 11% ammonia water according to a mass ratio of 1:1:2.5:9, uniformly mixing, and stirring at 25 ℃ and 250r/min for 2.5 hours to obtain the pretreated chopped basalt fiber; pretreating chopped basalt fiber, 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:0.35:0.45:9, uniformly mixing, adding allyl phosphine dichloride with the molar quantity of 0.92 times of 1, 3-bis (3-aminopropyl) tetramethyl disiloxane at a constant speed within 55min under the stirring condition of 3 ℃ and 250r/min in a nitrogen atmosphere, continuously stirring for 2.5h after the addition is finished, heating to 35 ℃, continuously stirring for reacting for 5h, mechanically separating, washing for 4 times with pure water, and drying for 9h at 65 ℃ to obtain modified chopped basalt fibers;
(3) The modified chopped basalt fiber, modified polypropylene and potassium persulfate are mixed according to the mass ratio of 1:8.5: and (3) uniformly mixing 0.015, placing in a double-screw extruder, melting, mixing and extruding at 195 ℃, placing in a die, die-pressing at 195 ℃ and 0.35MPa for 12s, keeping the pressure unchanged, cooling to 85 ℃, standing for 22h, and naturally cooling to room temperature to obtain the halogen-free high-temperature-resistant flame-retardant polymer material.
Comparative example 5
The preparation method of the halogen-free high-temperature-resistant flame-retardant polymer material mainly comprises the following preparation steps:
(1) Absolute ethyl alcohol and hydrochloric acid aqueous solution with mass fraction of 10% are mixed according to mass ratio of 1:2.5, uniformly mixing to prepare an acidic ethanol solution; uniformly mixing an equimolar amount of propylene alcohol and triisobutyl aluminum in a nitrogen atmosphere, stirring at-65 ℃ for 25min at 250r/min, heating to room temperature and continuously stirring for 3.5h to obtain a hydroxyl-protected monomer; the method comprises the steps of (1) mixing an M1810HA metallocene catalyst, 2, 6-di-tert-butyl-4-methylphenol and toluene according to a mass ratio of 1:0.35:7, uniformly mixing, and stirring at 25 ℃ and 250r/min for 25min to prepare a catalyst solution; in a nitrogen atmosphere, hydroxyl protecting monomers and toluene are mixed according to the mass ratio of 1:35, uniformly mixing, adding into a reaction container, stirring at 15 ℃ for 25min at 250r/min, introducing propylene to remove nitrogen, enabling the propylene pressure in the reaction container to reach and maintain at 0.12MPa, adding a catalyst solution with the mass of 0.035 times of that of toluene, stirring at 75 ℃ for 5h at 250r/min, pouring an acidic ethanol solution with the mass of 4.5 times of that of toluene after the reaction is finished, stirring at 20 ℃ for 25min at 250r/min, filtering, washing for 4 times by using absolute ethanol, and drying at 75 ℃ for 9h to obtain pre-modified polypropylene;
(2) In a nitrogen atmosphere, pre-modified polypropylene and toluene are mixed according to the mass ratio of 1:45, stirring for 12min at 75 ℃ at 250r/min, continuously stirring, adding maleic anhydride with the mass of 0.25 times of that of the pre-modified polypropylene at a constant speed within 25min, continuously stirring for 3.5h after the addition, pouring the mixture into pure water with the mass of 225 times of that of the pre-modified polypropylene after the reaction, stirring for 25min at 20 ℃ at 250r/min, filtering, washing for 4 times by absolute ethyl alcohol, and drying for 9h at 75 ℃ to obtain modified polypropylene;
(3) The preparation method comprises the following steps of (1) mixing chopped basalt fibers, modified polypropylene and potassium persulfate according to a mass ratio of 1:8.5: and (3) uniformly mixing 0.015, placing in a double-screw extruder, melting, mixing and extruding at 195 ℃, placing in a die, die-pressing at 195 ℃ and 0.35MPa for 12s, keeping the pressure unchanged, cooling to 85 ℃, standing for 22h, and naturally cooling to room temperature to obtain the halogen-free high-temperature-resistant flame-retardant polymer material.
Test examples
Testing of tensile Strength, high temperature resistance, anti-dripping Performance and flame retardant Property
Tensile strength test method: the halogen-free high-temperature-resistant flame-retardant polymer material obtained in each example and the comparative example material are tested according to GB/T1040.3 to obtain the halogen-free high-temperature-resistant flame-retardant polymer material with the tensile strength of 2mm/min.
High temperature resistant anti-molten drop: the halogen-free high temperature resistant flame retardant polymer material obtained in each example and the comparative example material were tested for melt index using a melt index tester according to ASTM-D1238-2010 standard at 230 ℃ under a load of 2.16kg.
The flame retardant performance test method comprises the following steps: the halogen-free high-temperature-resistant flame-retardant high polymer material obtained in each example and the comparative example material are tested for limiting oxygen index according to ISO4589-2 standard. The results are shown in Table 1.
As can be seen from the comparison of the experimental data of examples 1-3 and comparative examples 1-5 in Table 1, the halogen-free high-temperature-resistant flame-retardant polymer material prepared by the invention has good tensile strength, high-temperature-resistant anti-dripping performance and flame-retardant performance.
As can be found by comparing the data of examples 1-3 and comparative examples 1 and 2, the examples 1-3 have high tensile strength and low melt index, which indicates that the allyl alcohol is a polar monomer, the alcohol in the structure can act with the active center of the metallocene catalyst to inhibit the insertion of the monomer, so that the polymerization activity is reduced, the embedded copolymerization effect of the allyl alcohol is affected, the allyl alcohol is protected, the polymerization process can be better carried out, more hydroxyl groups are more easily connected, and the allyl alcohol can be combined with more maleic anhydride subsequently, so that the tensile strength and the high-temperature-resistant and anti-dripping performance are improved; similarly, 2, 6-di-tert-butyl-4-methylphenol is added into the catalyst liquid, so that the steric hindrance effect of the 2, 6-di-tert-butyl-4-methylphenol can be utilized, and the phenomenon that the system loses active polymerization characteristics due to chain transfer reaction caused by alkyl aluminum components in the metallocene catalyst is avoided, thereby improving the active polymerization of propylene and polar monomers, and more hydroxyl groups are more easily connected, so that the tensile strength and the high-temperature-resistant anti-dripping performance are improved.
The data comparison of examples 1-3 and comparative example 3 shows that the melt index of examples 1-3 is low, which indicates that the addition of vinyl pentamethyldisiloxane for copolymerization in the polymerization process of modified polypropylene introduces a silica structure, so that the thermal stability of the modified polypropylene is improved, and the high temperature resistance and the anti-dripping performance are further improved.
As can be seen from the comparison of the data of examples 1-3 and comparative example 4, examples 1-3 have high tensile strength and low melt index, which indicates that carboxyl and double bond are formed on modified polypropylene through modification by maleic anhydride, the carboxyl can be combined with amino groups on modified chopped basalt fibers electrostatically or is dehydrated to form amide combination, and the double bond can initiate polymerization of free radical unsaturated bonds through potassium persulfate to form a crosslinked network structure, so that the structure is more stable, and the tensile strength and the high-temperature-resistant and anti-dripping performance are improved.
The data comparison of examples 1-3 and comparative example 5 shows that examples 1-3 have high tensile strength, low melt index and high limiting oxygen index, which indicates that after the chopped basalt fiber is modified, dispersibility is improved, and a polyphosphazene organosilicon branched chain is generated on the surface of the chopped basalt fiber, contains a large amount of phosphorus, silicon and nitrogen elements, has good flame retardant property, amino groups on the polyphosphazene organosilicon branched chain can be combined with carboxyl groups on modified polypropylene polymerization, and double bonds on the polyphosphazene organosilicon branched chain can participate in polymerization of free radical unsaturated bonds to form a crosslinked network structure, so that flame retardant property, tensile strength and high temperature resistance and anti-molten drop property are improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (7)
1. The preparation method of the halogen-free high-temperature-resistant flame-retardant polymer material is characterized by comprising the following preparation steps:
(1) Uniformly mixing an equimolar amount of acrylic alcohol and triisobutyl aluminum in a nitrogen atmosphere, stirring for 20-30 min at-70 to-60 ℃ at 200-300 r/min, heating to room temperature, and continuously stirring for 3-4 h to obtain a hydroxyl-protected monomer; the method comprises the steps of mixing a metallocene catalyst, 2, 6-di-tert-butyl-4-methylphenol and toluene according to a mass ratio of 1:0.3 to 0.4: 6-8, uniformly mixing, and stirring for 20-30 min at the temperature of 20-30 ℃ and the speed of 200-300 r/min to prepare a catalyst solution; absolute ethyl alcohol and 8-12% hydrochloric acid aqueous solution in mass ratio of 1: 2-3, uniformly mixing to prepare an acidic ethanol solution; in a nitrogen atmosphere, hydroxyl protecting monomer, vinyl pentamethyl disiloxane and toluene are mixed according to the mass ratio of 1:1: mixing 30-40, adding the mixture into a reaction container, stirring at 10-20 ℃ for 20-30 min at 200-300 r/min, introducing propylene to remove nitrogen, enabling the propylene pressure in the reaction container to reach and be maintained at 0.11-0.13 MPa, adding a catalyst solution with the mass of 0.03-0.04 times of that of toluene, stirring at 70-80 ℃ for 4-6 h at 200-300 r/min, pouring an acidic ethanol solution with the mass of 4-5 times of that of toluene after the reaction is finished, stirring at 10-30 ℃ for 20-30 min at 200-300 r/min, filtering, washing 3-5 times by using absolute ethanol, and drying at 70-80 ℃ for 8-10 h to obtain pre-modified polypropylene;
(2) In a nitrogen atmosphere, pre-modified polypropylene and toluene are mixed according to the mass ratio of 1: uniformly mixing 40-50, stirring at 70-80 ℃ for 10-15 min at 200-300 r/min, continuously stirring, adding maleic anhydride with the mass of 0.2-0.3 times of that of the pre-modified polypropylene at a constant speed within 20-30 min, continuously stirring for 3-4 h after the addition, pouring the mixture into pure water with the mass of 200-250 times of that of the pre-modified polypropylene after the reaction is finished, stirring at 10-30 ℃ for 20-30 min at 200-300 r/min, filtering, washing for 3-5 times by using absolute ethyl alcohol, and drying at 70-80 ℃ for 8-10 h to obtain modified polypropylene;
(3) The preparation method comprises the following steps of (1) mixing chopped basalt fibers, 3-aminopropyl triethoxysilane, absolute ethyl alcohol and 10-12% ammonia water according to a mass ratio of 1:1: 2-3: uniformly mixing 8-10, and stirring at 20-30 ℃ and 200-300 r/min for 2-3 hours to obtain pretreated chopped basalt fibers; pretreating chopped basalt fiber, 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:0.3 to 0.4:0.4 to 0.6: 8-10, uniformly mixing, adding allyl phosphine dichloride with the molar weight of 0.9-0.95 times of that of 1, 3-bis (3-aminopropyl) tetramethyl disiloxane at a constant speed within 50-60 min under the stirring condition of 0-5 ℃ and 200-300 r/min in a nitrogen atmosphere, continuously stirring for 2-3 hours after the addition is finished, heating to 30-40 ℃, continuously stirring for reacting for 4-6 hours, mechanically separating, washing for 3-5 times by pure water, and drying for 8-10 hours at 60-70 ℃ to obtain modified chopped basalt fibers;
(4) The modified chopped basalt fiber, modified polypropylene and potassium persulfate are mixed according to the mass ratio of 1: 8-9: and (3) uniformly mixing 0.01-0.02, placing in a double-screw extruder, melting, mixing and extruding at 190-200 ℃, placing in a die, die pressing at 190-200 ℃ and 0.3-0.4 MPa for 10-15 s, keeping the pressure unchanged, cooling to 80-90 ℃, standing for 20-24 h, and naturally cooling to room temperature to obtain the halogen-free high-temperature-resistant flame-retardant polymer material.
2. The method for preparing a halogen-free high temperature resistant flame retardant polymer material according to claim 1, wherein the reaction process of the hydroxyl protecting monomer in the step (1) is as follows:
。
3. the method for preparing a halogen-free high temperature resistant flame retardant polymer material according to claim 1, wherein the metallocene catalyst in the step (1) is M1810HA;
wherein 2, 6-di-tert-butyl-4-methylphenol will combine the aluminum alkyl component of the metallocene catalyst as follows:
，
wherein R represents an alkyl group.
4. The method for preparing the halogen-free high-temperature-resistant flame-retardant polymer material according to claim 1, wherein the reaction process of the pre-modified polypropylene in the step (1) is as follows:
。
5. the method for preparing the halogen-free high-temperature-resistant flame-retardant polymer material according to claim 1, wherein the reaction process of the modified polypropylene in the step (2) is as follows:
。
6. the method for preparing the halogen-free high-temperature-resistant flame-retardant polymer material according to claim 1, wherein the chopped basalt fiber in the step (3) has a diameter of 12.7 μm, a length of 6mm and a linear density of 200tex.
7. A halogen-free high temperature resistant flame retardant polymer material prepared by the preparation method of the halogen-free high temperature resistant flame retardant polymer material according to claim 1.
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| CN102051017A (en) * | 2009-11-09 | 2011-05-11 | 赢创德固赛有限公司 | Thermoplastic elastomer mixtures |
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| JP2010132869A (en) * | 2008-10-28 | 2010-06-17 | Sanyo Chem Ind Ltd | Resin composition for molded article used for building material |
| CN102051017A (en) * | 2009-11-09 | 2011-05-11 | 赢创德固赛有限公司 | Thermoplastic elastomer mixtures |
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